Production of capillary active amine-amides



. ammonium chloride.

ylaminoethyl amine.

w 7 2,742,464 1 Patented Apr- 7 5 No Drawing. Application April,2,5, 1951, Serial No. 222,928 7 p 7 Claims. (Cl. zen-247.2

This invention relates to improved methods for the production of amine-amides and to certain novel amineamides produced thereby.

Capillary active cationic agents have found use in various industrial fields. Among other things they have been used as finishing agents for textiles, for precipitating and fixing pigments on textiles, for breaking petroleum emulsions, for discharging negatively charged particles in separatoryorfiltration-processes, and as bacteriostaticand bacteriocidal agents. Heretofore-the bulk of the commercially produced cationicagents have been long chain alkyl ammonium salts such .as lauryl benzyl dimethyl 7 However, among ,the :cationic agents available are a limited class of amine-amides derived lfrorn higher molecular weight. aliphatic or aliphatic- .aromatic acids, for example, oleoyl aminoethyl diethyl- .iamino methosulfate.

amides :have been prepared by condensing acarboxylic Generally speaking such amine- :acid thalide, and the like with asymmetrically substituted polyamines. For instance, oleoyl aminoethyl diethylamine 'methosnlfate is derived from; oleicacid and dieth- Among other things, such a process is lacking "in flexibility due to the very limited-ammber of commercially available asymmetricallysubstituted ipolyamines.

It is a principal object .of this invention to provide a very simple method for preparing capillary active ca tionic amine-amides.

It is another object of this invention to provide a method for preparing,capillaryzactive amine-amides without the necessity for using difiicultly prepared intermediates. I

It is a further object of this invention to provide a :method for preparing valuable capillary active aminearnides at mildly elevated .temp,era-tures and at atmos- -,-pheric pressures or without the necessity for using pressure vessels.

condensing an amide of an organiccarboxylic acid containing from nine to twenty-one carbon atoms in its acyl radical and containing a [3-hydroxy aliphatic substituent on its amide nitrogen atom with a phosphorus halide or-a sulfur oxy-halide and with an amine-forming compound including primary amines, secondary amines, tertiary amines, ammonia or ammonia deliveringl compoun'ds. The condensations and reactions of this invention take placeunder very mild heating and without the necessity for using pressure vessels. Normally, temperatures below 140 C. are adequate and most condensations take place readily at 130 C. or below, as at temperatures of 100 C. to- 120 C.

The amides usedin-the condensation reactions of this invention may be prepared by known methods, an .as that .disclosed in British .Patent 631,367 or by :the ,reac on of .carboxylic acids with appropriate amines or, ,hy:,tl 1e reaction of amides with appropriate ,alkylene oxides and the like. The acids from which :the amides are derived may be known cyclic or acyclic high molecular "weight carboxylic. acids having ,a sufficiently ,large hydrophobic molecular component .to produce the desired surface ace tivity and include such acids as aliphatic or aromaticaliphatic carboxylic acids-containing nine to -twentyvone carbon atoms. Especially valuable-productsarge from high molecular weight fatty: @CidS. The component is derived from p-hydroxy aliphatic primary .or secondary amines. Suitable primary gaminesaeaglily available commercially I include monoethanolamine, anonopropanol amine, monobutanolarnine a le-hydrous, I phenyl ethylamine. Presently .commerciallvavailahle fihydroxy aliphatic secondary .aminesdnclude such compounds as methyl ethanol amine, ethyl ethanol amine,

and diethanol amine, 1

The {halogenated :amine radical of :thisrinvention may be derived from a great evarietylof lmownprimargnsecondary, or tertiary amines or from ammonia or com:

pounds yielding-ammonia such-as .urea orzhexamethyilene tetramine or the "like. The flexibility .oii-the process of this invention .is apparent from the fact that :halides'of primaryiamines may.be;produced from ammonia or am- .monia delivering compounds, secondary samine halides .It is a special object of this invention to provide a 7 very flexible process for producing surface active vamine- .amides adapted for the productionof anydesired type of amine radicals varying from primary amine compounds,

.to quaternary ammonium compounds.

"It is an additional object of this inventionto provide a 7 ,method for producing surface active amine-amides in f ishiy It is another special object of this invention to' produce.

new classes of and certain specific surface active amineamides.

It is a further special objectofthis invention to ,provide a method for producing surface active amine-amides containing heterocyclic amines such as those derived from pyridine or morpholine.

Other, objects, features .and .advantages of this :invene ;tion:be.apparent fromrthe more :detailed description twhich IfOllOWS.

:In accordance :with this invention .a wide .varietyuof valuable capillary active amine-amides are produced by from primary amines, ttertiary amine vhalides from =se'condary amines, and quaternary-ammonium halides 'from tertiary amines.

By known methods :the corresponding base may be separated or isolatedfrom the L-halide-saIt, -and salts ofthe base with other acids readily prepared. Likewise, by

known methods, the halide may'be replaced'by other salt-' forming radicals.

,Thus the process of this tinvention proyidesa method for producing salts iof-the general :formula-z R; R. il/ RCO.NR|.CH:.QHR2,N

wherein R is a saturated or unsaturated cyclic or acyclic "hydrocarbon radical containing 8 -to 20 carbon atoms;

R1 and R2 are Hora substituted or unsubstituted hydrocarbon radical, advantageously "an alkyl radical; (R-3,5114 andRsai-e the same or .-ditferent and represent H'ror substituted or unsubstituted hydrocarbon radicals-advantageously substitutedor unsubstituted ialkyl radicals; 1R3, R4 and R5 may conjointly representtazheterocyclic secondary or tertiarynitrogen base such as pyridine, morpholine or nicotine, and X'is ahalide or other anion. Y

The high yields and .:puri*tyof the products o'f the process of thisninvention have been determined'by surface active titration as disclosed by T. Barret al. in hisarticle The determination 50f surface active agents in solution" in Society of Chemical Industry Journal, vol. 67, Feb- 3 ruary 1948, pp. 45-48. The technique has been modified so that in the titration the dye passes from the aqueous to the chloroform phase. In the titration, pure recrystallized sodium dodecyl sulfate and a methylene blue solution (0.04% in 20% alcohol) were used as reagents. An M/ 1000 solution of the sodium dodecyl sulfate was made (0.288 gram per liter). Also a suitable quantity of the substance being tested was likewise weighed and water added to give about 1 liter of the solution thereby forming approximately an M/ 1000 solution. A preliminary rough estimate may be necessary to ascertain the appropriate weight of substance to be used. Ten mls. of this solution was transferred by pipette to a 50 ml. stoppered bottle and 1 ml. of

HCl, 20 mls. of CHaCl and 4 drops of methylene blue solution were added. The solution was then titrated with an M/ 1000 sodium dodecyl sulfate solution under vigorous shaking until the aqueous layer was completely colorless. The approach of the complete disappearance of color was indicated by the rapidity of the separation of the two layers after shaking. At the completion of the titration both layers separated bright and clear. The titration was sensitive to about 0.2 ml. in an M/ 1000 solution.

Complementary discussions of surface active titrations will be found in the following articles.

Association of Official Agricultural Chemists Journal, vol. 28, 1945. General colorimetric method for determination of small quantities of sulfonated or sulfated surface active compounds by J. H. Jones, pp. 398-409.

Industrial and Engineering Chemistry (Analytical Edition), vol. 15, 1943 (July-December). Germicidal quaternary ammonium salts in dilute solution" by M. E. Auerbach, pp. 492-493.

Industrial and Engineering Chemistry (Analytical Edition), vol. 16, 1944 (July-December). Colorimetric assay of quaternary ammonium salts by M. Auerbach, p. 739.

Royal Society of London Proceedings, vol. 168, Series A (Mathematical and Physical Sciences), November 7, 1938. Determination of the paraffin-chain radical by G. S. Hartley and D. F. Runnicles, pp. 424-425.

The Journal of the Society of Dyers and Colourists, vol. 61, July, 1945. Tensimetric analysis of surfaceactive electrolytes by J. M. Preston, pp. 165-166.

The following examples in which the yields were determined by surface active titration as described herein further illustrate the practice of our invention.

Example 1 Two hundred and thirty-four parts of B-hydroxy ethyl lauramide prepared according to British Patent No. 631,367 are warmed to 60 C. and 46 parts of phosphorus trichloride are gradually mixed. The reaction is mildly exothermic, and gentle cooling may be applied. Then 79 parts of pyridine are added to the mixture and the mixture is heated to 120 C. and maintained at about 120 C. for two hours. As the reaction proceeds the quaternary salt forms and the mixture sets to a viscous mass. The reaction product may be purified by crystallization from alcohol/ether mixtures. The product is readily soluble in water, alcohol and similar polar solvents.

The yield of commercial lauroyl aminoethyl pyridinium chloride, having the formula was 90% of the theoretical amount.

iii

Example 2 While keeping the temperature below 50 by external cooling, 119 parts of thionylchloride are gradually introduced into 339 parts of N methyl N-fi-hydroxy ethyl oleoylamide, prepared by conventional methods or by the process of amidation outlined in British Patent No. 631,367. Then 87 parts of morpholine are introduced and the mixture is heated to C. and maintained at about 130 C. for one and a half hours. The viscous reaction product is clearly soluble in water, but the free base may be precipitated from the solution by the addition of alkali. By treatment of the tertiary base thus obtained with dimethyl or diethyl sulphate, benzyl chloride or other alkyl halides, the tertiary base may be converted to a quaternary salt.

The yield of commercial oleoyl N.methyl N.ethyl morpholinium hydrochloride having the formula was 70% of the theoretical amount.

Example 3 Ninety-three parts of phosphorous tribromide are gradually added at 40 C. to a solution of 341 parts fl-hydroxy propylstearamide (prepared from hardened whale oil and mono-isopropanolamine by the process of catalytic amidation outlined in British Patent No. 631,367, or by conventional methods such as the condensation of stearic acid with mono-propanolamine or the condensation of stearamide with propylene oxide) in 300 parts of toluene. Then 146 parts of diethylamine are added and the mixture is heated in an autoclave to 130 C. and maintained at about 130 C. for approximately two hours. Upon cooling, crystalline diethylamine salts separate and may be removed by filtration, or washed out with water leaving the tertiary base in toluene solution. Thus diethylamine-propylstearamide may then be obtained by the distillation of the solvent.

The yield of commercial stearoyl aminoisopropyl diethylaminc hydrobromide, having the formula was 50% of the theoretical amount.

Example 4 Forty-five parts of phosphorous trichloridc are added to 253 parts of mixed ethanolamides prepared from palm kernel oil by the method described in British Patent No. 631,367. A mixture of parts dodecylamine and 25 parts of alcohol is then added and the reaction mass is heated under gentle reflux for three hours. The final product is freed from the solvent. lt readily disperses in water to form a milky solution, from which the secondary base, a mixed acylaminoethyl dodecylamine is precipitated by the addition of alkali.

The yield of palm kernel fatty acid aminoethyl laurylamine hydrochloride, having as a principal ingredient a compound of the formula CHa(CHa)m.C0.NH.GHz.OHa.NBZ(CnH1s).HCl

was 60% of the theoretical amount.

Example 5 Two hundred and fifty-three parts of the B-hydroxy ethanolamide, prepared from palm kernel oil, in 200 parts of benzene are treated with 137 parts of phosphorous triiodide, prepared in situ, from iodine and red phosphorous.

' mage med tate is as,.. a .stifi paste, which he yield of palm 'kernel fatty acid aminoeth'yl pyridinium iodide, having as a principle ingredient a compound of the formula I OH-CH was 80% of the theoretical amount.

Example 6 One hundred and five parts of diethylamine are added to 253 parts of the fi-hydroxy ethanolamide, prepared from coconut oil as previously described in British Patent No. 631,367 at60 C. Then 46 parts of phosphorous trichloride are gradually introduced with external cooling, and after the addition has been completed the mixture is heated to 130 C. and maintained at about 130 C. for approximately three hours. The tertiary base obtained may be isolated from the hydrochloride in the usual manner by the addition of alkali.

The yield of coconut fatty acid amino ethyl diethylamine hydrochloride, having as a principle ingredient a compound of the formula CH2.(CH2)10.CO.NH.CH2.CH2.N(C2H5)2.HCl was 55% of the theoretical yield.

Example 7 amide prepared from fl-hydroxy ethyl lauramide and phosphorous trichloride as described in Example 1. Then the mixture is warmed to 130 C. and maintained at that temperature for about three hours. The aminoethyl ,lauramide may be isolated in the usual way from the reaction mixture.

. A principal ingredient of the capillary active amineamide is lauroyl aminoethyl amine hydrochloride having the formula The practice of this invention has been exemplified in the specification by various details and examples. It will be understood, however, that these details may be varied widely and that substitutions, additions or omissions can be made without departing from the spirit or the scope of the invention which is intended to be defined by the appended claims.

What is claimed is:

. nitrogen compound being effected by reacting under atmospheric pressure and heating to elevated temperatures in excess of 100 C. but not exceeding 140C.

2. A process for producing capillary active amineamides which comprises mixing an amide of a fatty acid containing from nine to twenty-one carbon atoms in its acyl radical and containing a fi-hydroxy ethylol substituent on its nitrogen atom, with a compound selected from the 1. A process for producing capillary active amine-J amides which comprises condensing an amide of a fatty group consisdng', qf,nhqp .lorus halides and sulfur oxyhalides, said halides'beingselected from thegroup consistcompound selectedirom the group consisting o'f ammonia,

compounds .delivering ammonia :81 elevated temperatures,

iprimary amines, secondary amines, 18nd tertiary amines, and heating the formed mixture to a temperature exceeding 100 C. but not exceeding 140 C. replacing said hydroxy substituent with a halogenated amine radical.

3. A process for producing capillary active amineamides which comprises condensing an amide of a fatty acid containing from9 to 21 carbon atoms in its acyl radical and containinga fi-hydroxy alkanol substituent on .its amide nitrogen atom with a phosphorus halide, said halide being selected from the group consisting of chlo rides, iodides and bromides and with a nitrogen compound selected from the group consisting of ammonia, compounds delivering ammonia at elevated temperatures, primary amines, secondary amines and tertiary amines, said condensation with said nitrogen compound taking place respectively in approximately the molar ratios of l: l/ 3 :1 and being effected by reactions taking place under atmospheric pressure and heating at elevated temperatures exceeding 100 C. but not exceeding 140 C.

4. A process for producing capillary active amineamides which comprises mixing an amide of a fatty acid containing from nine to twenty-one carbon atoms in its acyl radical and containing a fi-hydroxy alkanol substituent on its nitrogen atom, with a compound selected from the group consisting of phosphorus halides and sulfur oxy-halides, said halides being selected from the group consisting of chlorides, iodides and bromides and with a cyclic nitrogen base, and heating the formed mixture to a temperature exceeding 100 C. but not exceeding 140 0. replacing said hydroxy substituent with a halogenated cyclic amine radical.

5. A process for producing capillary active amineamides which comprises mixing an amide of a fatty acid containing from nine to twenty-one carbon atoms in its acyl radical and containing a fl-hydroxy alkanol substituent on its nitrogen atom, with a compound selected from the group consisting of phosphorus halides and sulfur oxy-halides, said halides being selected from the group consisting of chlorides, iodides and bromides and with pyridine, and heating the formed mixture to a temperature exceeding 100 C. but not exceeding 140 C. replacing said hydroxy substituent with a halogenated amine radical.

6. A process for producing capillary active amineamides which comprises mixing an amide of a fatty acid containing from nine to twenty-one carbon atoms inits acyl radical and containing a B-hydroxy alkanol substituent on its nitrogen atom, with a compound selected from the group consisting of phosphorus halides and sulfur oxy-halides, said halides being selected from the group consisting of chlorides, iodides and bromides and with morpholine, and heating theformed mixture to a tem perature exceedinglOO" C. but not exceeding 140 C. replacing said hydroxy substituent with a halogenated morpholinium radical.

7. A process for producing capillary active amineamides which comprises mixing an amide of a fatty acid containing from nine to twenty-one carbon atoms in its uent on its amine nitrogen atom with a compound selected from the group consisting of phosphorus halides and sulfur oxy-halides, said halides being selected from the group consisting of chlorides, iodides and bromides and witha tertiary amine to produce the quaternary ammonium halide, and heating the formed mixture to a temperature exceeding C. but not exceeding C. replacing said hydroxy substituent with r a halogenated quaternary ammonium radical.

(References on following page) References Cited in the file of this patent UNITED STATES PATENTS Wirth Aug. 27, 1940 8 Haack May 20, 1941 Maxwell Oct. 21, 1941 'Henke et a1 Dec. 30, 1941 Bock May 12, 1942 Kaplan Sept. 17, 1946 

1. A PROCESS FOR PRODUCING CAPILARY ACTIVE AMINEAMIDES WHICH COMPRISES CONDENSING AN AMIDE OF A FATTY ACID CONTAINING FROM NINE TO TWENTY-ONE CARBON ATOMS IN ITS ACYL RADICAL AND CONTAINIG A B-HYDROXY ALKANOL SUBSITUTENT ON ITS AMIDE NITROGEN ATOM WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF PHOSPHORUS HALIDES AND SULFUR OXYHALIDES, SAID HALIDES BEING SELECTED FROM THE GROUP CONSISTING OF CHLORIDES, IODIDES AND BROMIDES AND WITH A NITROGEN COMPOUND SELECTED FROM THE GROUP CONSISTING OF AMMONIA, COMPOUND DELIVERING AMMONIA AT ELEVATED TEMPERATURES, PRIMARY AMINES, SECONDARY AMINES, AND TERTIARY AMINES, SAID CONDENSATIONS WITH SAID NITROGEN COMPOUND BEING EFFECTED BY REACTING UNDER ATMOSPHERIC PRESSURE AND HEATING TO ELEVATED TEMPERATURES IN EXCESS OF 100* C. BUT NOT EXCEEDING 140* C. 